Abstract:

A method for protecting tobacco from, during, comprises the step of
covering the tobacco with a material, preferably a net, which has a
protective activity against the harmful organisms.

Claims:

1-9. (canceled)

10. A method for protecting tobacco from harmful organisms during storage,
comprising covering tobacco with a material having a protective activity
against harmful organisms, wherein said material is a netting having a
mesh size of no greater than 1.5.times.1.5 mm.

11. The method of claim 10, wherein said material is a textile material, a
plastic material, a leather material, a flocked fabric, a sheeting, foil,
a packaging material, or a cellulose containing material.

12. The method of claim 10, wherein said material is treated with a
composition comprising:a. at least one pesticide (component A), andb. at
least one polymeric binder (component B).

13. The method of claim 12, wherein said composition comprises, based on
the total weight of component A and component 3, from 0.001 to 95 weight
% of said at least one pesticide and from 5 to 99.999 weight % of said at
least one polymeric binder.

14. The method of claim 12, wherein said at least one pesticide is
selected from the group consisting of pyrethroid compounds, carbamate
compounds, organophosphorous compounds, N-arylhydrazine derivatives,
molluscicides, rodenticides, and fungicides.

16. The method of claim 15, wherein said polymeric binder is selected from
the group consisting of optionally partially or completely hydrolyzed
poly(styrene-acrylates), poly(styrene-butadiene), optionally partially or
completely hydrolyzed ethylene-acrylate-copolymers, and optionally
partially or completely hydrolyzed ethylene-vinylacetate-copolymers.

17. The method of claim 12, wherein said polymeric binder is an acrylic
binder, obtained by radical polymerization of at least one monomer of
formula II ##STR00025## whereinR20 and R21 independently are H,
linear or branched, optionally fluoro-substituted C1- to
C10-alkyl, or optionally substituted aryl; andR22 independently
is linear or branched, optionally fluoro-substituted C1- to
C10-alkyl, or optionally substituted aryl.

23. The method of claim 21, wherein R20, R21, and R22
independently are phenyl or tolyl.

24. A device for protecting tobacco from harmful organisms comprising a
device for storing tobacco and a material for covering the stored
tobacco, wherein said material has a protective activity against harmful
organisms and is a netting having a mesh size of no greater than
1.5.times.1.5 mm.

Description:

[0001]The invention relates to a method of protecting tobacco, tobacco
bales or other tobacco products from harmful organisms during harvesting,
drying, curing, transport and storage. The invention further relates to a
device for carrying out the method.

[0002]Tobacco is a valuable cash crop, and is the most widely grown
non-food crop in the world. After harvesting, the tobacco leaves are
subjected to the stages of curing, fermenting and aging as part of the
process of producing tobaccos suitable for smoking or chewing by humans.
All of these stages require extended storage periods, in the last case up
to several years. During these storage periods, the tobacco leaves have
to be protected from pests, specifically from insect pests.

[0003]Nevertheless, contamination of the tobacco with pesticides has to be
avoided to create no additional health hazards for the human consumers.

[0004]Currently, a common method of pest control in the storage of tobacco
is the use of gaseous pesticides, specifically methyl bromide and
phosphin (PH3). However, the use of methyl bromide is not desirable
from an ecological point of view as this substance is ozone depleting.
Phosphine, on the other hand, is highly toxic and--if not properly
handled--is a potential health hazard for the workers engaged in the
production of tobacco.

[0005]Accordingly, there is a continuous demand to provide new methods for
protecting tobacco leaves from harmful organisms, while avoiding
pesticide residues in the tobacco and health hazards for the workers.

[0006]It has now been found that this demand can be met by providing a
method for protecting tobacco from harmful organisms during storage
comprising the step of covering the tobacco with a material which has a
protective activity against the harmful organisms.

[0007]WO 2005/064072 discloses a composition for the impregnation of
fibers, fabrics and nettings imparting a protective activity against
pests, however, the use of such a composition for protecting tobacco is
not contemplated.

[0008]According to the invention, tobacco can be protected from harmful
organisms in an easy and efficient way without health hazard to workers
and without causing residues of pesticides in the tobacco products.

[0009]In a further aspect of the invention there is provided the use of a
material which has a protective activity against harmful organisms for
protecting tobacco.

[0010]In yet a further aspect of the invention there is provided a device
for protecting tobacco from harmful organisms comprising a device for
storing the tobacco and a material which has a protective activity
against harmful organisms, for covering the tobacco.

[0011]The term "tobacco" as used herein means tobacco plants or parts
thereof in any stage after and during harvesting, specifically in the
stages of curing, fermentation and aging.

[0012]The terms "protection" or "protecting" as used herein means a
controlling or repelling action.

[0013]The term "harmful organism" as used herein means pests, specifically
arthropod pests, including insects and arachnids, and harmful
micro-organisms, specifically fungi including spores, microbes and
viruses.

[0014]The term "covering" as used herein means that the fabric or netting
forms a physical barrier between the tobacco to be protected and the
harmful organism, but does not imply that the tobacco is in physical
contact with the cover material.

[0015]The material is preferably a non-rigid material. It is preferably a
textile material or plastics material selected from the group consisting
of yarn, fibers, fabric, knitgoods, nonwovens, netting material, foils,
tarpaulins and coatings. The netting material may be prepared by any
method known in the art, for example by circular knitting or warp
knitting, or by sewing parts of a netting to obtain the desired nettings.

[0016]The textile material or plastics material may be made form a variety
of natural and synthetic fibers, also as textile blends in woven or
non-woven form, as knit goods, yarns or fibers. Natural fibers are for
example cotton, wool, silk or bast fibers, like jute, linen, ramie, hemp
and kenaf. Synthetic fibers are for example polyamides, polyesters,
polyacryl nitrites, polyolefines, for example polypropylene or
polyethylene, Teflon, and mixtures of fibers, for example mixtures of
synthetic and natural fibers. Polyamides, polyolefins and polyesters are
preferred. Polyethylene terephthalate is especially preferred.

[0018]Further, the term material includes cellulose-containing materials
e.g. cotton materials such as garment or cotton nets and also wooden
materials such as houses, trees, board fences, or sleepers and also
paper.

[0019]Preferably, the material is a textile material or plastics material,
e.g. polypropylene, polyethylene, polyester or polyamide.

[0020]Preferably the textile material is a netting.

[0021]Suitable mesh sizes, shapes (like squares, rectangles or diamonds)
and patterns are well known to those skilled in the art and may be chosen
in view of the size of the prevailing pests. While the mesh size should
be small enough to present an obstacle to the pest it is usually
preferred to have an exchange of air and humidity.

[0022]Suitable dimensions of the mesh sizes (side length of a mesh) are in
the range of 5 mm, preferably 2.5 mm, more preferred 1.5 mm as an upper
limit and 0.1 mm, preferably 0.25 mm, more preferred 0.5 mm, in
particular 0.75 mm as a lower limit. In the case of very small pests a
wide-meshed woven fabric may be preferred as a textile material.

[0023]More preferred are nettings made from polyester, especially
polyethylene terephthalate. In a further preferred embodiment the
material is a cellulose containing material.

[0024]Preferably, the material is treated with a composition comprising a
pesticide, however, the invention is not limited to such embodiments.
E.g., the pesticide can also be incorporated into a fiber during the
production of the fiber.

[0025]Such materials show good results in controlling the pests and
provide long lasting protection to the stored tobacco.

[0026]In a preferred embodiment, the pesticide is incorporated into the
material (e.g. into the plastics matrix) or applied to the surface of the
material or both.

[0027]In a most preferred embodiment, the material is treated with a
composition comprising:

[0028]The pesticidal composition comprises in general 0.001 to 95% by
weight preferably 0.1 to 45% by weight, more preferably 0.5 to 30% by
weight, most preferably 0.5 to 25% by weight, based on the weight of the
composition, of at least one pesticide.

[0029]The pesticidal composition preferably comprises the following
components, based on the solids content of the composition [0030]a) 0.1
to 45% by weight, preferably 0.5 to 30% by weight, more preferably 1 to
25% by weight of at least one pesticide (component A), and [0031]b) 55 to
99% by weight, preferably 70 to 98% by weight, more preferably 75 to 90
by weight of at least one polymeric binder (component B),wherein the sum
of the components is 100% by weight of solids content of the insecticide
composition.

[0032]In a further preferred embodiment the pesticidal composition
comprises the following components, based on the solids content of the
composition, [0033]a) 20 to 70% by weight, preferably 25 to 65% by
weight, more preferably 30 to 65% by weight of at least one pesticide
(component A), and [0034]b) 30 to 80% by weight, preferably 35 to 75% by
weight, more preferably 35 to 70 by weight of at least one polymeric
binder (component B),wherein the sum of the components is 100% by weight
of solids content of the pesticidal composition.

[0035]The term "pesticide" as used herein comprises insecticides,
repellents and fungicides. The term "insecticides" as used herein
comprises agents with arthropodicidal (specifically, insecticidal,
acaricidal and miticidal), molluscicidal and rodenticidal activity, if
not otherwise stated in the context.

[0036]The term "fungicides" as used herein comprises agents with
fungicidal, microbicidal and viricidal activity, if not otherwise stated
in the context.

[0037]Preferably, the pesticide is an insecticide or repellent.

[0038]The pesticidal composition is particularly suitable for application
to polyester nettings as used for mosquito nets.

[0039]The pesticidal composition of the present invention may be applied
to textile materials or plastics material, before their formation into
the desired products, i.e. while still a yarn or in sheet form, or after
formation of the desired products.

Pesticide (Component A)

[0040]Preferably, the pesticide is an insecticide and/or repellent with a
fast paralyzing or killing effect of the insect and low mammalian
toxicity. Suitable insecticides and/or repellents are known by a person
skilled in the art. Suitable insecticides and repellents are disclosed
e.g. in E. C. Tomlin et al., The Pesticide Manual, 13ed., The British
Crop Protection Council, Farnham 2003, and the literature cited therein.

[0112]Insecticides with a sterilising effect on adult mosquitoes such as
[0113]1-(alfa-(chloro-alpha-cyclopropylbenzylidenamino-oxy)-p-tolyl)-3-(2-
,6-difluorobenzoyl)urea, [0114]Diflubenzuron:
N-(((3,5-dichloro-4-(1,1,2,2-tetrafluoroethoxy)phenylamino)carbonyl)2,6
difluoro benzamid, [0115]Triflumuron:
2-Chloro-N-(((4-(trifluoromethoxy)phenyl)-amino-)carbonyl)benzamide, or a
triazin such as N-cyclopropyl-1,3,5-triazine-2,4,6-triamin; and
[0116]Lambda-cyhalothrine:
α-cyano-3-phenoxybenzyl-3-(2-chloro-3,3,3-trifluoroprop-1-enyl)-2,2-
-dimethylcyclopropane carboxylate, as a 1:1 mixture of (Z)-(1R,3R),
R-ester and (Z)-(1S,3S), S-ester.

[0119]Suitable rodenticides are first generation anticoagulant
rodenticides and second generation anticoagulant rodenticides, where
second generation rodenticides are preferred. Examples for first
generation anticoagulant rodenticides are warfarin, chlorphacinone,
coumatetralyl, suitable second generation anticoagulant rodenticides are
for example flocoumafen, brodifacoum, difenacoum, bromadialone,
difethialone, and bromethalin.

[0121]In a further preferred embodiment, the pesticide is at least one
N-arylhydrazine derivative, preferably of formula I,

##STR00001##

wherein

A is C--R2 or N;

B is C--R3 or N;

D is C--R40 or N;

[0122]with the proviso that at least one of A, B or D must be other than
N;Z is halogen, CN, NO2, C1-C6-alkyl,
C1-C6-haloalkyl, C1-C6-alkoxy or
C1-C6-haloalkoxy;n is an integer of 0, 1 or 2;

Q is

##STR00002##

[0123]wherein

R is

[0124]hydrogen;C1-C10-alkyl, optionally substituted with one or
more halogens; C3-C6-cycloalkyl; C1-C4-alkoxy;
C1-C4-haloalkoxy; (C1-C4-alkyl)SOx;
(C1-C4-haloalkyl)SOx; phenyl, optionally substituted with
one to three halogen, C1-C4-alkyl, C1-C4-haloalkyl,
C1-C4-alkoxy, C1-C4-haloalkoxy,
(C1-C4-alkyl)SOx, (C1-C4-haloalkyl)SOx,
NO2 or CN groups; phenoxy, optionally substituted with one to three
halogen, C1-C4-alkyl, C1-C4-haloalkyl,
C1-C4-alkoxy, C1-C4-haloalkoxy,
(C1-C4-alkyl)SOx, (C1-C4-haloalkyl)SOx,
NO2 or CN groups;C3-C12-cycloalkyl, optionally substituted
with one or more halogens, C1-C6-alkyl,
C1-C6-haloalkyl, C1-C4-alkoxy,
C1-C4-haloalkoxy, (C1-C4-alkyl)SOx,
(C1-C4-haloalkyl)SOx; phenyl, optionally substituted with
one to three halogen, C1-C4-alkyl, C1-C4-haloalkyl,
C1-C4-alkoxy, C1-C4-haloalkoxy, NO2 or CN
groups; phenoxy, optionally substituted with one to three halogen,
C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy,
C1-C4-haloalkoxy, NO2 or CN groups;orphenyl, optionally
substituted with one or more halogens, C1-C4-alkyl,
C1-C4-haloalkyl, C1-C4-alkoxy,
C1-C4-haloalkoxy, NO2 or CN groups;or

CR17R18R19;

[0125]R17 and R18 are each independently C1-C6-alkyl,
C3-C6-alkenyl, C3-C6-alkynyl, or
C3-C6-cycloalkyl which may be substituted with 1 to 3 halogen
atoms;R19 is hydrogen or C1-C6-alkyl;R1 and R7
are each independently hydrogen or C1-C4-alkyl;R5 and
R6 are each independentlyhydrogen;C1-C10-alkyl, optionally
substituted with one or more halogen, hydroxy, C1-C4-alkoxy,
(C1-C4-alkyl)SOx, CONR8R9, CO2R10,
R11, R12;C3-C10-alkenyl, optionally substituted with
one or more halogen, hydroxy, C1-C4-alkoxy,
(C1-C4-alkyl)SOx, CONR8R9, CO2R10,
R11, R12;C3-C10-alkynyl, optionally substituted with
one or more halogen, hydroxy, C1-C4-alkoxy,
(C1-C4-alkyl)SOx, CONR8R9, CO2R10,
R11, R12;C3-C12-cycloalkyl, optionally substituted
with one or more halogen, hydroxy, C1-C4-alkoxy,
(C1-C4-alkyl)SOx, CONR8R9, CO2R10,
R11, R12;C3-C6-cycloalkyl, optionally substituted
with one to three halogen, C1-C4-alkyl,
C1-C4-haloalkyl, C1-C4-alkoxy,
C1-C4-haloalkoxy, NO2 or CN groups;phenyl, optionally
substituted with one or more halogen, C1-C4-alkyl,
C1-C4-haloalkyl, C1-C4-alkoxy,
C1-C4-haloalkoxy, NO2 or CN groups;pyridyl, optionally
substituted with one or more halogen, C1-C4-alkyl,
C1-C4-haloalkyl, C1-C4-alkoxy,
C1-C4-haloalkoxy, NO2 or CN groups;R5 and R6 may
be taken together to form a ring represented by the structure

[0127]R13, R14, R15 and R16 are each independently
hydrogen or C1-C4-alkyl;

X is O, S or NR15;

[0128]X1 is chlorine, bromine or fluorine;r is an integer of 0 or 1;p
and m are each independently an integer of 0, 1, 2 or 3, with the proviso
that only one of p, m or r can be 0 and with the further proviso that the
sum of p+m+r must be 4, 5 or 6;x is an integer of 0, 1 or 2; orthe
enantiomers or the salts thereof.

[0129]In a preferred embodiment Q in formula I is

##STR00006##

[0130]More preferably, the least one N-arylhydrazine derivative is a
compound of formula Ia

##STR00007##

whereinR4 is chlorine or trifluoromethyl;Z1 and Z2 are each
independently chlorine or bromine;R6 is C1-C6-alkyl,
C3-C6-alkenyl, C3-C6-alkynyl, or
C3-C6-cycloalkyl which may be substituted with 1 to 3 halogen
atoms, or C2-C4-alkyl which is substituted by
C1-C4-alkoxy;R17 and R18 are each independently
C1-C6-alkyl, C3-C6-alkenyl, C3-C6-alkynyl,
or C3-C6-cycloalkyl which may be substituted with 1 to 3
halogen atoms;R19 is hydrogen or C1-C6-alkyl;or
enantiomers or salts thereof.

[0131]In the definition of formula I and formula Ia shown above, the
substituents have the following meanings:

[0133]"Alkoxy" refers to a straight-chain or branched alkyl group having 1
to 4 carbon atoms (methyl, ethyl, propyl, 1-methylethyl, butyl,
1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl) bonded through an
oxygen linkage, at any bond in the alkyl group. Examples include methoxy,
ethoxy, propoxy, and isopropoxy.

[0135]With respect to the intended use of the compounds of formula I,
particular preference is given to the following meanings of the
substituents, in each case on their own or in combination:

[0136]Preference is given to compounds of formula I wherein R4 is
trifluoromethyl.

[0137]Preference is further given to compounds of formula I wherein
Z1 and Z2 are both chlorine.

[0138]Moreover, preferred are compounds of formula I wherein R6 is
C1-C6-alkyl, especially ethyl.

[0139]Preference is further given to compounds of formula I wherein
R17 and R18 are both methyl.

[0140]Moreover, preferred are compounds of formula I wherein R17 and
R18 form a cyclopropyl ring which is unsubstituted or substituted by
1 to 3 halogen atoms, especially chlorine and bromine.

[0141]Moreover, particularly preferred are compounds of formula I wherein
R17 and R18 form a cyclopropyl ring which is substituted by 2
halogen atoms.

[0142]Moreover, particularly preferred are compounds of formula I wherein
R17 and R18 form a cyclopropyl ring which is substituted by 2
chlorine atoms.

[0143]Particularly preferred are compounds of formula I wherein R17
and R18 form a 2,2-dichlorocyclopropyl ring.

[0144]Preference is further given to compounds of formula I wherein
R19 is C1-C6 alkyl, especially methyl.

[0145]Particularly preferred are compounds of formula I wherein R17,
R18 and R19 are all methyl.

[0146]Moreover, particularly preferred are compounds of formula I wherein
R17, R18 and R19 form a moiety
1-methyl-2,2-dichlorocyclopropyl.

[0147]Preference is further given to compounds of formula I wherein

R4 is trifluoromethyl;Z1 and Z2 are each independently
chlorine or bromine;R6 is C1-C6-alkyl;R17 and
R18 are C1-C6-alkyl or may be taken together to form
C3-C6-cycloalkyl which is substituted by 1 to 2 halogen
atoms;R19 is C1-C6-alkyl;or the enantiomers or salts
thereof.

[0148]Particular preference is given to
N-ethyl-2,2-dimethylpropionamide-2-(2,6-dichloro-α,α,α--
trifluoro-p-tolyl)hydrazone and
N-ethyl-2,2-dichloro-1-methylcyclopropane-carboxamide,
2-(2,6-dichloro-α,α,α-trifluoro-p-tolyl)hydrazone.

[0149]Furthermore, particular preference with respect to the use in the
present invention is given to the compound of formula Ia-1
(N-ethyl-2,2-dimethylpropionamide-2-(2,6-dichloro-α,α,α-
-trifluoro-p-tolyl)-hydrazone):

##STR00008##

[0150]Moreover, particular preference with respect to the use in the
present invention is given to the compound of formula Ia-2
(N-Ethyl-2,2-dichloro-1-methylcyclo-propanecarboxamide-2-(2,6-dichloro-.a-
lpha.,α,α-tri-fluoro-p-tolyl)hydrazone):

##STR00009##

[0151]With respect to their use, particular preference is given to the
compounds Ia-A compiled in the tables below. Moreover, the groups
mentioned for a substituent in the tables are on their own, independently
of the combination in which they are mentioned, a particularly preferred
embodiment of the substituent in question.

[0152]With respect to their use, particular preference is also given to
the hydrochloric acid, maleic acid, dimaleic acid, fumaric acid,
difumaric acid, methane sulfenic acid, methane sulfonic acid, and
succinic acid adducts of the compounds of the tables below.

[0153]Preferred insecticides and/or repellents of the pesticidal
composition of the invention may be either one or a mixture. Preferred
mixtures of pesticides are mixtures of insecticides and/or repellents
with similar diffusion/migration properties. This group of insecticides
and/or repellents may include synthetic pyrethroids such as
alphacypermethrin, cyfluthrin, deltamethrin, etofenprox and permethrin,
other pyrethroids such as bifenthrine, and non-pyrethroids such as
carbosulphane.

[0154]The pesticide can also be included in the pesticidal composition as
one of a water-based pesticide concentrate or a solvent, preferably an
organic solvent, based pesticide concentrate or a concentrate based on a
mixture of water and a solvent, preferably an organic solvent.
Water-based concentrates may be in the form of suspensions or dispersions
comprising suitable dispersing agents if necessary or in the form of
emulsions comprising emulsifiers, solvents and co-solvents if
appropriate. Nanoparticular pesticidal formulations may be obtained by
dissolving solid solutions of pesticidal in a polar organic solvent, e.g.
poly vinyl pyrrolidone (PVP). The concentration of the pesticide in the
water based or solvent based concentrates is in general between 0.5 to
60%, preferably 1 to 40%, more preferably 3 to 20%.

[0155]The particle size of the pesticide in water-based suspensions or
dispersions is in general between 50 nm to 20 μm, preferably 50 nm to
8 μm, more preferably 50 nm to 4 μm, most preferably 50 nm to 500
nm, or 1 μm to 3 μm.

Polymeric Binder (Component B)

[0156]The polymeric binder (component B) may be any polymeric binder known
in the art. Especially preferred are polymeric binders used in the area
of impregnating or coating textile materials or plastics materials.

[0159]The conditions and further necessary and suitable components for the
preparation of suitable polymers by polymerization, preferably radical
polymerization, of the monomers mentioned above are known by a person
skilled in the art.

[0160]Suitable polymeric binders obtained by polymerization, preferably
radical polymerization, of the above-mentioned monomers are homopolymers
or copolymers, preferably selected from the group consisting of
polyacrylates, polymethacrylates, polyacrylonitrile, polymaleic acid
anhydride, polystyrene, poly(methyl)styrene, polybutadiene,
polyvinylacetate, polyvinylalcohol as well as copolymers obtained by
polymerization of at least two different ethylenically unsaturated
monomers of the group of monomers mentioned above and blends of said
homopolymers and/or copolymers, for example poly(styrene-acrylates),
poly(styrene-butadiene), ethylene-acrylate-copolymers,
ethylene-vinylacetate-copolymers, which may be partially or completely
hydrolyzed.

[0170]More preferably R20 is H or methyl, R21 is H and R22
is methyl, ethyl, n-butyl or 2-ethylhexyl.

[0171]Most preferably the monomer of formula II (component BA) is selected
from the group consisting of 2-ethylhexylacrylate, n-butylacrylate,
methylacrylate, methylmethacrylate and ethylacrylate. Most preferably a
copolymer obtainable by polymerization of at least two different acrylic
monomers of formula II is employed.

[0172]Most preferably an acrylic binder is used as component B obtainable
by emulsion polymerization of [0173]b1a) at least one monomer of formula
II as component B1A

[0180]wherein [0181]R23, R24, R25 and R26 are
independently selected from the group consisting of H, C1- to
C10-alkyl which may be linear or branched, for example, methyl,
ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, tert-butyl,
n-pentyl, i-pentyl, sec-pentyl, neo-pentyl, 1,2-dimethylpropyl, i-amyl,
n-hexyl, i-hexyl, sec-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl and
n-decyl; preferably R23, R24, R25 and R26 are
selected from the group consisting of H, C1- to C4-alkyl, which
may be linear or branched, for example methyl, ethyl, n-propyl,
iso-propyl, n-butyl, i-butyl, sec-butyl and tert-butyl; substituted or
un-substituted aryl, preferably substituted or unsubstituted C6- to
C10-aryl, more preferably substituted or unsubstituted C6-aryl,
for example phenyl or tolyl; [0182]more preferably R23 is H or
methyl, R24, R25 and R26 are preferably H; [0183]most
preferably R23 is H or methyl and R24, R25 and R26
are H; [0184]b1c) optionally at least one monomer of formula IV as
component B1C

##STR00014##

[0185]wherein [0186]R27 and R28 are independently selected from
the group consisting of H, C1- to C10-alkyl which may be linear
or branched, for example, methyl, ethyl, n-propyl, i-propyl, n-butyl,
i-butyl, sec-butyl, tert-butyl, n-pentyl, i-pentyl, sec-pentyl,
neo-pentyl, 1,2-dimethylpropyl, i-amyl, n-hexyl, i-hexyl, sec-hexyl,
n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl and n-decyl; preferably R27
and R28 are selected from the group consisting of H, C1- to
C4-alkyl, which may be linear or branched, for example methyl,
ethyl, n-propyl, iso-propyl, n-butyl, i-butyl, sec-butyl and tert-butyl;
substituted or unsubstituted aryl, preferably substituted or
unsubstituted C6- to C10-aryl, more preferably substituted or
unsubstituted C6-aryl, for example phenyl or tolyl; [0187]most
preferably R27 and R28 are H; [0188]X is selected from the
group consisting of H, OH, NH2, OR29OH, glycidyl,
hydroxypropyl,

[0197]The acrylic binder is preferably obtainable by emulsion
polymerization of [0198]b1a) 10 to 95% by weight, preferably 30 to 95% by
weight, more preferably 50 to 90% by weight of component B1A; [0199]b1b)
1 to 5% by weight of component B1B; [0200]b1c) 0 to 5% by weight,
preferably 1 to 4% by weight, more preferably 0.2 to 3% by weight of
component B1C; [0201]b1d) further monomers which are copolymerizable with
the monomers mentioned above selected from [0202]b1d1) 0 to 30% by
weight, preferably 0 to 25% by weight, more preferably 5 to 20% by weight
of component B1D1; and/or [0203]b1d2) 0 to 40% by weight, preferably 0 to
30% by weight, more preferably 5 to 20% by weight of component
B1D2;wherein the sum of the components B1A, B1B and optionally B1C and
B1D is 100% by weight.

[0204]In a further preferred embodiment the acrylic binder is obtainable
by emulsion polymerization of

b1a) 10 to 95% by weight, preferably 30 to 95% by weight, more preferably
50 to 90 by weight of at least one acrylic binder (component B1A) as
defined above, comprising; [0205]b1a1) 10 to 90% by weight, preferably
15 to 85% by weight, more preferably 30 to 85% by weight based on the
acrylic binder of n-butyl acrylate; [0206]b1a2) 10 to 90% by weight,
preferably 12 to 85% by weight, more preferably 15 to 65% by weight based
on the acrylic binder of at least one monomer of formula II, different
from n-butyl acrylate;b1b) 1 to 5% by weight based on the acrylic binder
of at least one monomer of formula III (component B1B);b1c) 0 to 5% by
weight, preferably 0.1 to 4% by weight, more preferably 0.2 to 3% by
weight based on the acrylic binder of at least one monomer of formula III
(component B1C);b1d) further monomers which are copolymerizable with the
monomers mentioned (component B1D) above selected from [0207]b1d1) 0 to
30% by weight, preferably 0 to 25% by weight, more preferably 5 to 20% by
weight based on the acrylic binder of at least one polar monomer,
preferably (meth)acrylic nitrile and/or methyl(meth)acrylate (component
B1D1); and/or [0208]b1d2) 0 to 40% by weight, preferably 0 to 30% by
weight, more preferably 5 to 20% by weight based on the acrylic binder of
at least one non polar monomer, preferably styrene and/or a-methylstyrene
(component B1D2);wherein the sum of the components B1A, B1B and
optionally B1C and B1D is 100% by weight.

[0209]The acrylic binder may comprise further additives as known by a
person skilled in the art, for example film forming agents and
plasticizers, e.g. adipate, phthalate, butyl diglycol, mixtures of
diesters preparable by reaction of dicarboxylic acids and alcohols which
may be linear or branched. Suitable dicarboxylic acids and alcohols are
known by a person skilled in the art.

[0210]The insecticide compositions comprising the binder as claimed in the
present invention are wash resistant while permitting continuous release
of the insecticide at a controlled rate, in order to provide the required
bioavailability of the insecticide. It is not necessary to add for
example a dispersing agent that, after application of the composition to
a fabric and upon welting of the fabric, reduces the hydrophobicity
imparted to the insecticide by the binder to permit limited insecticide
release. Preferably, the insecticide composition of the present invention
does therefore not comprise a dispersing agent in addition to the
polymeric binder.

[0211]Most preferably the acrylic binder is obtainable by emulsion
polymerization of the following components:

b1a) 50 to 90% by weight of at least one monomer of formula II as
component B1A

##STR00017##

[0212]wherein [0213]R20 is H or methyl, R21 is H and R22 is
methyl, ethyl, n-butyl, or 2-ethylhexyl, as component B1A, most
preferably component B1A is 2-ethylhexylacrylate, n-butylacrylate,
methylacrylate, methylmethacrylate or ethylacrylate; [0214]b1b) 1 to 5%
by weight of at least one monomer of formula III

##STR00018##

[0215]wherein R23 is H or methyl, R24, R25 and R26
each are H as component B1B; [0216]b1c) 1 to 10% by weight, preferably
1 to 7% by weight, more preferably 2 to 5% by weight of at least one
monomer of formula IV

##STR00019##

[0217]wherein R27 and R28 are H and X is H, OH, NH2,
OR29OH, glycidyl or a group of the formula

##STR00020##

[0218]wherein [0219]R30 is selected from the group consisting of
C1- to C10-alkyl which may be branched or linear, for example
methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl,
tert-butyl, n-pentyl, i-pentyl, sec-pentyl, neo-pentyl,
1,2-dimethylpropyl, i-amyl, n-hexyl, i-hexyl, sec-hexyl, n-heptyl,
n-octyl, 2-ethylhexyl, n-nonyl, n-decyl; preferably C1- to
C4-alkyl, which may be branched or linear, for example methyl,
ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl and
tert-butyl; substituted or unsubstituted aryl, preferably substituted or
unsubstituted C6- to C10-aryl, more preferably substituted or
unsubstituted C6-aryl, for example phenyl or tolyl; [0220]R29
is selected from the group consisting of C1- to C10-alkylene,
for example methylene, ethylene, propylene, butylene, pentylene,
hexylene, heptylene, octylene, nonylene, decylene; preferably C1- to
C4-alkylene, for example methylene, ethylene, propylene, butylenes;
substituted or unsubstituted arylenes, preferably substituted or
un-substituted C6- to C10-arylene, more preferably substituted
or unsubstituted C6-arylene, for example phenylene; [0221]as
component B1C, most preferably X is acetoacetyl; [0222]b1d) further
monomers which are copolymerizable with the monomers mentioned above
selected from [0223]b1d1) 0 to 30% by weight, preferably 0 to 25% by
weight, more preferably 5 to 20% by weight of component B1D1, preferably
(meth)acrylic nitrile and/or methyl(meth)acrylate; [0224]and/or
[0225]b1d2) 0 to 40% by weight, preferably 0 to 30% by weight, more
preferably 5 to 20% by weight of component BD2, preferably styrene and/or
a-methylstyrene;wherein the sum of components BA, BB and optionally BC
and BD is 100% by weight.

[0226]In a further most preferred embodiment the amount of n-butylacrylate
as component BA is from 30 to 90% by weight, and the other components B1B
and optionally a further monomer of formula II (component B1A), B1C and
B1D are chosen as mentioned before, wherein the sum of components B1A,
B1B and optionally B1C and B1D is 100% by weight.

[0227]The acrylic binder of the present invention is preferably obtainable
by emulsion polymerization of the monomers mentioned before. Suitable
process conditions are known by a person skilled in the art, and are
disclosed e.g., in WO-A 2005/064072.

[0228]In the acrylic binder according to the invention, it is possible to
add in general up to 10% by weight, preferably 0.05 to 5% by weight of
mono- or di-olefinically unsaturated monomers containing reactive or
cross-linking groups. Examples of such monomers are in particular the
amides of α,β-olefinically unsaturated C3-5-carboxylic
acids, particularly acryl amides, methacryl amides and maleic diamides,
and their N-methylol derivatives such as N-methylol acrylic amide,
N-methylol methacrylic amide, N-alkoxy methyl amides of
α,β-monoolefinically unsaturated C3-5-carboxylic acids
such as N-methoxy methacrylic amide and N-n-butoxymethylacrylic amide,
vinyl sulfonic acid, monoesters of acrylic and methacrylic acids with
alkanediols such as glycol, butanediol-1,4, hexane diol-1,6, and
3-chloropropanediol-1,2, and also allyl and methallyl esters of
α,β-olefinically unsaturated mono- and di-carboxylic acids
such as diallyl maleate, dimethyl allyl fumarate, allyl acrylate and
allyl methacrylate, diallyl phthalate, diallyl terephthalate, p-di-vinyl
benzene, methylene-bis-acrylamide and ethylene glycol di-allylether.

[0229]The molecular weight of the non crosslinked emulsion polymers
obtained is in general 40,000 to 250,000 (determined by GPC). The
molecular weight is usually controlled by the use of conventional chain
stoppers in conventional amounts. Conventional chain stoppers are for
example sulfoorganic compounds.

[0230]The acrylic binder of the present invention is obtained in form of
its aqueous dispersion and is preferably employed in the insecticide
compositions of the present invention in form of the aqueous dispersion.

Polyurethane Binders and/or Polyisocyanurate Binders (Component B2)

[0231]In a further preferred embodiment the polymeric binders are
polyurethanes and/or polyisocyanurates. Said polyurethanes and/or
polyisocyanurates may be employed either alone as polymeric binders or in
combination with further polymeric binders, especially polymeric binders
mentioned before, for example in combination with the acrylic binders
mentioned before.

[0237]The polyurethane is preferably obtainable by reaction of the
following components: [0238]b2a) 55 to 99% by weight, preferably 70 to
98% by weight, more preferably 75 to 90 by weight based on the
polyurethane of at least one diisocyanate or polyisocyanate (component
B2a), preferably aliphatic, cycloaliphatic, araliphatic and/or aromatic
insocyanates, more preferably diisocyanates, which are optionally
biuretisized and/or isocyanurized, more preferably alkylene diisocyanates
having from 4 to 12 carbon atoms in the alkylene unit, like 1,12-dodecane
diisocyanate, 2-ethyltetramethylene
diisocyanate-1,4,2-methylpentamethylene diisocyanate-1,5, tetramethylene
diisocyanate-1,4, lysinester diisocyanate (LDI), hexamethylene
diisocyanate-1,6 (HMDI), cyclohexane-1,3- and/or -1,4-diisocyanate, 2,4-
and 2,6-hexahydro-toluoylene diisocyanate as well as the corresponding
isomeric mixtures 4,4'-2,2'- and 2,4'-dicyclohexylmethane diisocyanate as
well as the corresponding mixtures,
1-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl cyclohexane (IPDI), 2,4-
and/or 2,6-toluoylene diisocyanate, 4,4'-, 2,4' and/or
2,2'-diphenylmethane diisocyanate (monomeric MDI),
polyphenylpolymethylene polyisocyanate (polymeric MDI) and/or mixtures
comprising at least 2 of the isocyanates mentioned before; further
ester-, urea-, allophanate-, carbodiimid-, uretdione- and/or urethane
groups comprising di- and/or polyisocyanates may be used; most preferably
1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylene cyclohexane (IPDI) and
hexamethylene diisocyanate-1,6 (HMDI); [0239]b2b) 10 to 90% by weight,
preferably 12 to 85% by weight, more preferably 15 to 65% by weight based
on the polyurethane of at least one diol, triol or polyol (component
B2B), preferably aliphatic, cycloaliphatic and/or araliphatic diols
having 2 to 14, preferably 4 to 10 carbon atoms, more preferably polyols,
selected from the group consisting of polyetherols, e.g.
polytetrahydrofurane, polyesterols, polythioetherpolyols, hydroxyl group
containing polyacetales and hydroxyl group containing aliphatic
polycarbonates or mixtures of at least 2 of the polyols mentioned before.
Preferred are polyesterols and/or polyetherols. The hydroxyl number of
the polyhydroxy compounds is in general from 20 to 850 mg KOH/g and
preferably 25 to 80 mg KOH/g. Further, diols and/or triols having a
molecular weight of from in general 60 to <400, preferably from 60 to
300 g/mol are employed. Suitable diols are aliphatic, cycloaliphatic
and/or araliphatic diols having from 2 to 14, preferably 4 to 10 carbon
atoms, e.g. ethylene glycol, propane diol-1,3, decane diol-1,10, o-, m-,
p-dihydroxycyclohexane, diethylene glycol, dipropylene glycol and
preferably butane diol-1,4, neopentyl glycol, hexane diol-1,6 and
bis-(2-hydroxy-ethyl)hydroquinone, triols, like 1,2,4-,
1,3,5-trihydroxy-cyclohexane, glycerine and trimethylol propane and
mixtures of low molecular hydroxyl groups containing polyalkylene oxides
based on ethylene oxide and/or 1,2-propylene oxide and the diols and/or
triols mentioned before; [0240]b2c) 0 to 10% by weight, preferably 0.1 to
5% by weight, more preferably 1 to 5% by weight based on the polyurethane
of further components (component B2C), preferably adipic acid or carbonyl
diimidazole (CDI); and [0241]b2d) 0 to 10% by weight, preferably 0.1 to
5% by weight, more preferably 0.5 to 5% by weight based on the
polyurethane of further additives (component B2D);wherein the sum of the
components B2A, B2B, B2C and B2D is 100% by weight.

[0242]The polyurethanes are prepared by methods known in the art. Further,
additives as known by a person skilled in the art may be used in the
process for preparing the polyurethanes. Component B may also be a
polyisocyanurate or a mixture of a polyisocyanurate and a polyurethane,
preferably a polyurethane as mentioned above.

[0243]Polyisocyanurates are polymers comprising groups of the following
formula:

##STR00021##

wherein R* is an alkylene or arylene residue depending on the isocyanate
employed in the preparation of the isocyanurate.

[0244]Polyisocyanurates are usually prepared by cyclotrimerization of
isocyanates. Preferred isocyanates are the same isocyanates as mentioned
before (component B2A). Preparation processes and conditions for the
preparation of polyisocyanurates are known by a person skilled in the
art.

Pesticidal Compositions

[0245]The pesticidal compositions of the invention may be aqueous
compositions or dry compositions, i.e. compositions which do not comprise
water.

[0246]In a preferred embodiment the pesticidal compositions are aqueous
compositions, preferably comprising 55 to 97% by weight, more preferably
85 to 95% by weight of water, and 3 to 45% by weight, preferably 5 to 15%
by weight of solids, based on the total of the components in the
insecticide compositions of the present invention, wherein the total is
100% by weight. The solids are preferably selected from the group
consisting of at least one pesticide as component A as defined above, and
at least one polymeric binder as component B as defined above, and
optionally at least one fixative agent as component C as defined below,
and optionally further components depending on the use of the final
product as defined above.

[0247]The treatment baths from which the pesticidal compositions are
applied to the material are preferably aqueous formulations comprising 95
to 99.5% by weight, preferably 95 to 99% by weight, more preferably 97 to
99% by weight of water, and 0.5 to 5% by weight, preferably 1 to 5% by
weight of solids, based on the total of the components in the
insecticidal compositions of the present invention. The solids are
preferably selected from the group consisting of at least one pesticidal
of formula I as component A as defined above, and at least one polymeric
binder as component B as defined above, and optionally at least one
fixative agent as component C as defined below, and optionally further
components depending on the use of the final product as defined above.

[0248]The polymeric binder may advantageously be applied with a fixative
agent C for improved attachment of the pesticide on the material. The
fixative agent may comprise free isocyanate groups.

[0250]More preferably the isocyanurate is a isocyanurate which is
hydrophilized with a polyalkylene oxide based on ethylene oxide and/or
1,2-propylene oxide, preferably polyethylene oxide.

[0251]The isocyanurate used as a fixative agent can be prepared by methods
known in the art. Preferably 5 to 25% by weight, more preferably 7 to 20%
by weight, most preferably 10 to 15% by weight of the isocyanate groups
based on the amount of isocyanate used as staring material for the
preparation of the isocyanurate are free isocyanate groups.

[0252]Most preferably the isocyanurate used as a fixative agent is
dissolved in a polar aprotic solvent, e.g. THF, DMF or propylene or
ethylene carbonate.

[0253]The most preferred fixative agent used is an isocyanurate based on
HMDI which are hydrophilized with a polyethylene oxide and which is
dissolved in propylene carbonate (70% by weight of HMDI in 30% by weight
of propylene carbonate). The amount of free isocyanate groups is 11 to
12% by weight, based on the amount of isocyanate used as staring material
for the preparation of the isocyanurate.

[0254]The pesticidal composition preferably comprises the following
components, based on the solids content of the composition, if a fixative
agent is used: [0255]a) 20 to 70% by weight, preferably 25 to 65% by
weight, more preferably 30 to 65% by weight of at least one pesticide
(component A), and [0256]b) 29 to 72% by weight, preferably 34 to 70% by
weight, more preferably 33 to 66 by weight of at least one polymeric
binder (component B) as defined above; [0257]c) 1 to 8% by weight,
preferably 1 to 5% by weight, more preferably 2 to 4% by weight of at
least one fixative agent (component C);wherein the sum of the components
is 100% by weight of solids content of the pesticide composition.

[0260]Typical pigments used in the pestidical compositions of the present
invention are pigments which are used in pigment dyeing or printing
processes or are applied for the coloration of plastics and are known by
a person skilled in the art.

[0261]Pigments may be inorganic or organic by their chemical nature.
Inorganic pigments are mainly used as white pigments (e.g., titanium
dioxide in the form of rutile or anatas, ZnO, chalk) or black pigments
(e.g., carbon black). Colored inorganic pigments may be used as well but
are not preferred because of potential toxicologic hazards. For imparting
color, organic pigments or dyestuffs are preferred. Organic pigments may
be mono or disazo, naphthol, benzimidazolone, (thio) indigoid, dioxazine,
quinacridone, phthalocyanine, isoindolinone, perylene, perinone, metal
complex or diketo pyrrolo pyrrole type pigments. Pigments may be used in
powder or liquid form (i.e., as a dispersion). Preferred pigments are
Pigment Yellow 83, Pigment Yellow 138, Pigment Orange 34, Pigment Red
170, Pigment Red 146, Pigment Violet 19, Pigment Violet 23, Pigment Blue
15/1, Pigment Blue 15/3, Pigment Green 7, Pigment Black 7. Other suitable
pigments are known to a person skilled in the art.

[0262]Typical dyestuffs which may be used in the present invention are vat
dyes, cationic dyes and disperse dyes in powder or liquid form. Vat dyes
may be used as pigments or following the vatting (reduction) and
oxidation procedure. Using the vat pigment form is preferred. Vat dyes
may be of the indanthrone type, e.g. C.I. Vat Blue 4, 6 or 14; or of the
flavanthrone type, e.g. C.I. Vat Yellow 1; or of the pyranthrone type,
e.g. C.I. Vat Orange 2 and 9; or of the isobenzanthrone (isoviolanthrone)
type, e.g. C.I. Vat Violet 1; or of the dibenzanthrone (violanthrone)
type, e.g. C.I. Vat Blue 16, 19, 20 and 22, C.I. Vat Green 1, 2 and 9,
C.I. Vat Black 9; or of the anthraquinone carbazole type, e.g. C.I. Vat
Orange 11 and 15, C.I. Vat Brown 1, 3 and 44, C.I. Vat Green 8 and C.I.
Vat Black 27; or of the benzanthrone acridone type, e.g. C.I. Vat Green 3
and 13 and C.I. Vat Black 25; or of the anthraquinone oxazole type, e.g.
C.I. Vat Red 10; or of the perylene tetra carbonic acid diimide type,
e.g. C.I. Vat Red 23 and 32; or imidazole derivatives, e.g. C.I. Vat
Yellow 46; or amino triazine derivatives, e.g. C.I. Vat Blue 66. Other
suitable vat dyes are known by a person skilled in the art.

[0263]Typical disperse and cationic dyestuffs are known by a person
skilled in the art.

[0264]If cellulosic substrates are employed as material, said cellulosic
substrates are preferably dyed with vat, direct, relative or sulphur
dyestuffs.

[0265]In a further embodiment the pesticidal compositions of the present
invention are pesticidal compositions as mentioned before comprising at
least one pigment and/or at least one dyestuff. The pesticidal
compositions of the present invention preferably comprise 10 to 300% by
weight, more preferably 20 to 150% by weight of the pigment and/or
dyestuff relating to the total weight of the solids content of the
pesticide.

[0266]The material, for example textile material or plastics material, may
be impregnated prior to use if the composition is delivered in the form
of a kit.

[0267]In a further embodiment, the impregnated material according to the
present invention further comprises one or more components selected from
preservatives, detergents, stabilizers, agents having UV-protecting
properties, optical brighteners, spreading agents, anti-migrating agents,
foam-forming agents, welting agents, anti-soiling agents, thickeners,
further biocides, plasticizers, adhesive agents, pigments and dyestuffs.
Suitable examples of the components mentioned above are known to a person
skilled in the art.

[0268]In a further embodiment of the present invention the impregnated
material comprises besides the at least one pesticide and the at least
one polymeric binder as described before at least one pigment and/or at
least one dyestuff. The amount of the at least one pigment is in general
from 0.05 to 10% by weight, preferably 0.1 to 5% by weight, more
preferably 0.2 to 3.5% by weight of the (dry) weight of the non-living
material. The amount of the at least one dyestuff is in general from 0.05
to 10% by weight, preferably 0.1 to 5% by weight, more preferably 0.2 to
3.5% by weight of the (dry) weight of the material. The material
comprises preferably either at least one pigment or at least one
dyestuff. Suitable pigments and dyestuffs are mentioned before.

Process for Impregnation of a Protective Material

[0269]In a further embodiment, the present invention relates to a process
for impregnation of a material, for example a textile material or
plastics material, comprising [0270]i) forming an aqueous formulation or
a melt, wherein an aqueous formulation is preferred, comprising at least
one pesticide and at least one polymeric binder, preferably a polymeric
binder as defined above, and optionally further ingredients; [0271]ii)
applying the aqueous formulation to the material by [0272]iia) passing
the material through the aqueous formulation; [0273]or [0274]iib)
bringing the material in contact with a roller that is partly or fully
dipped into the aqueous formulation and drawing the aqueous formulation
to the side of the material in contact with the roller, [0275]or
[0276]iic) double-side coating of the material [0277]or [0278]iid)
spraying the aqueous formulation onto the material, wherein the spraying
is carried out with any suitable device for spraying by hand or
automatically, for example with an aerosol can or devices usually used in
a factory; [0279]or [0280]iie) applying the aqueous formulation in form
of a foam; [0281]or [0282]iif) submerging the material into the aqueous
formulation; [0283]or [0284]iig) brushing the aqueous formulation onto or
into the material; [0285]or [0286]iih) pouring the aqueous formulation
onto the material; [0287]or [0288]applying the melt by calendaring or
with a doctor-blade; [0289]iii) optionally removing surplus aqueous
formulation or surplus; and [0290]iv) drying and/or curing the material.

[0291]In the context of the invention, an aqueous formulation may be a
solution, an emulsion or a suspension/dispersion.

[0292]The aqueous formulation or the melt preferably comprises the
pesticidal composition, which is preferably employed in form of an
aqueous formulation.

[0293]In the context of the invention "impregnation" is a process for
applying the pesticidal composition. This process may include a process
for curing the applied pestidical composition to achieve a coating onto
the material, if desired. An "impregnated material" is a material onto
which the pesticidal composition is applied. The "impregnated material"
may be coated by curing the applied pesticidal composition, if desired.

[0294]The pesticidal composition may also be applied onto the material by
transfer printing, inkjet printing, a screen process, and powder
printing.

[0295]Details of the application of the pesticidal composition are well
known to someone skilled in the art and are disclosed, e.g., in WO
2005/064072.

[0296]The method according to the invention is useful for protecting
tobacco, tobacco bales or other tobacco products. It can be used for
protecting any kind of tobacco, such as e.g. tobacco produced from
Nicotiana rostica and Nicotiana tabacum, specifically dark tobacco,
bright tobacco, burley tobacco, shade tobacco and Perique.

[0297]The method is useful for protecting, the tobacco from any kind of
pests and disease encountered in the transport and storage of tobacco,
specifically from storage pests, like bugs, beetles and moths, mites,
mice and tobacco diseases.

[0300]The method according to the invention is specifically useful for the
control of the cigarette beetle (Lasioderma serricorne), and the tobacco
moth (Ephespha elutella), the two main pests in tobacco storage.

[0301]The methods according to the invention can be applied in all stages
and types of tobacco processing, where a storage period is required.

[0302]Such processing includes the curing of tobacco after harvesting,
specifically the yellowing, leaf drying and stem drying stage.

[0303]It includes any type of curing, such as air-curing, sun-curing,
fire-curing and, in particular, flue-curing. In the flue-curing, the
method can be used in direct-fired systems as indirect fired systems,
working, e.g., with heat exchangers.

[0304]The method according to the invention is further useful in the
fermenting and aging steps of tobacco processing. Depending on the kind
and quality of the final tobacco product, these steps range from a couple
of days to several years--during which the tobacco has to be protected
from pests.

[0305]Accordingly, the method according to the invention is useful in the
production of any kind of tobacco product for human consumption, such as
cigarettes, cigars, pipe tobacco, cigarette tobacco, snuff, chewing
tobacco, snuff, gutka and creamy snuff.

[0306]The device according to the invention comprises means for spreading
out the tobacco leaves, such as a rack or an open framework where sticks
of tied leaves or the whole stalk is hung, a material, which has
protective activity against harmful organism, and which covers the
tobacco to be protected, and, optionally means for attaching the material
to the means for spreading out the tobacco.

[0307]The material is preferably a net, because this does not disturb the
drying or curing process--which requires an exchange of air, humidity and
heat between the tobacco and its environment--while it still affords good
protection against pests.

[0308]Surprisingly, the use of nets leads to a good protection even in the
case of fungal diseases.

[0309]The invention is further illustrated by the following examples
without limiting it thereby.

EXAMPLES

I. Binder

A) Preparation of Polymer Dispersions

General Procedure:

[0310]250 g of water and 3 g of a styrene seed (33% by weight) having a
medium particle diameter of 30 nm are heated to 85° C. and 5% by
weight of feed 2 are added. After 10 min. addition of feed 1 comprising
the monomers mentioned below and feed 2 is started.

[0318]Aqueous polymer dispersions comprising FI-1 polymerizable photo
initiator which is later useful as crosslinking agent is a photo
initiator of formula

##STR00024##

whereinR8 is an organic radical having from 1 to 30 carbon
atoms,R9 is H or a methyl group, andR10 is a phenyl group which
is optionally substituted or a C1- to C4-alkyl group.

II. Examples of use

a) Preparation of Long-Lasting Insecticidal Nets (LLINs)

[0319]The insecticidal treatment was performed with aqueous dispersions
according to examples A1-A17 on commercially available white polyester
netting material (fiber titer 75 denier, 156 mesh (about 2×2 mm,
diamond shape), weight 28-32 g/m2) without prior washing. The
aqueous treatment baths were prepared by mixing the aqueous dispersions
with commercially available emulsions of insecticide and/or repellent,
setting pH with buffer solutions and adding a fixative (if needed). The
concentrations of the treatment baths were adjusted according to the
liquor uptake possible (LU between 60 and 100%). The treatment baths were
applied by using a padder-stenter equipment on a laboratory scale (Mathis
AG, Switzerland). The netting material is fully immersed into the
treatment bath and excess liquor is removed by passing it through
cylinders which move in counter-direction. By choosing a defined distance
between these cylinders (and thus a defined pressure) the liquor uptake
can be controlled. The liquor uptake is measured by weighing an
impregnated piece of netting and subtracting the weight of the dry,
untreated netting and is given as % weight of liquor on weight of
netting. The drying/curing step was performed in a laboratory stenter
which allows to control the temperature and time of the treatment.

b) Testing Methodologies

Limited Forced Exposure Assay:

[0320]Alphacypermethrin-impregnated long-lasting insecticidal nets (LLINs,
200 mg ai/m2) were cut to fit 150×25 mm Petri dishes. LLINs
were placed on the bottom of the dishes and 10 adult cigarette beetles,
Lasioderma serricome, were introduced into each dish onto the nets.
Beetles were exposed to the nets for 10, 30, or 60 minutes and the nets
were then removed. Mortality/knockdown was evaluated at the time of net
removal. Ten replicates were performed per treatment.

Behavioral Assay:

[0321]Cardboard shipping tubers (457 mm pieces of 76 mm diameter) were
covered on one end with alphacypermethrin-impregnated long-lasting
insecticidal net (LLIN, 200 mg ai/m2), which was secured with a
rubber band and electrical tape. The end of the tube with the LLIN was
attached to a clear plastic cup (76 mm diameter×89 mm height) with
electrical tape filled with 20.0 g of toasted oat cereal to serve as a
food source. Ten adult tobacco moths, Ephestia elutella, (Table 3) or ten
adult cigarette beetles, Lasioderma serricorne, (Table 2) were introduced
into the tubes on the opposite end of the LLIN and food source. The
opposite (open) end of each tube was then sealed. Location and mortality
of the moths/beetles were evaluated at 1 and 2 days (E. elutella) or 1
and 4 days (L. serricorne) after treatment (DAT). Ten replications were
performed per treatment with E. elutella and eight replications were
performed per treatment with L. serricorne.

[0323]2. LLINs caused significantly greater mortality of cigarette
beetles (93% at 1 day after treatment (DAT) and 100% at 4 DAT) compared
to the untreated net in a behavioral assay where the beetles had to pass
through the net to reach a food/light source:

[0324]3. LLINs caused significantly greater mortality of tobacco moths
(89% at 1 DAT and 94% at 2 DAT) compared to the untreated net in a
behavioral assay where the moths had to pass through the net to reach a
food/light source. Very few moths able to pass through the untreated net
or LLIN, indicating utility of (2 mm×2 mm) LLINs for use as a
physical and chemical barrier for protection of stored tobacco from
tobacco moth infestations (Table 3, FIG. 4):

[0325]4. LLINs caused significantly greater mortality of to cigarette
beetles compared to the untreated net in a behavioral assay where the
beetles had to pass through the net to reach a food/light source. No
beetles were able to pass through the untreated net or LLIN, indicating
utility of (1 mm×1 mm) LLINs at different a.i. levels for use as a
physical and chemical barrier for protection of stored tobacco cigarette
beetle infestations (Table 4, FIG. 5):